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External cycling regenerating nitrogen oxides (NOx ≡ NO + NO2) from their oxidative reservoir, NOz, is proposed to reshape the temporal-spatial distribution of NOx and consequently hydroxyl radical (OH), the most important oxidant in the atmosphere. Here we verify the in situ external cycling of NOx in various environments with nitrous acid (HONO) as an intermediate based on synthesized field evidence collected onboard aircraft platform at daytime. External cycling helps to reconcile stubborn underestimation on observed ratios of HONO/NO2 and NO2/NOz by current chemical model schemes and rationalize atypical diurnal concentration profiles of HONO and NO2 lacking noontime valleys specially observed in low-NOx atmospheres. Perturbation on the budget of HONO and NOx by external cycling is also found to increase as NOx concentration decreases. Consequently, model underestimation of OH observations by up to 41% in low NOx atmospheres is attributed to the omission of external cycling in models.

The interaction between water vapor and atmospheric aerosol leads to enhancement in aerosol water content, which facilitates haze development, but its concentrations, sources, and impacts remain largely unknown in polluted urban environments. Here, we show that the Indian capital, Delhi, which tops the list of polluted capital cities, also experiences the highest aerosol water yet reported worldwide. This high aerosol water promotes secondary formation of aerosols and worsens air pollution. We report that severe pollution events are commonly associated with high aerosol water which enhances light scattering and reduces visibility by 70%. Strong light scattering also suppresses the boundary layer height on winter mornings in Delhi, inhibiting dispersal of pollutants and further exacerbating morning pollution peaks. We provide evidence that ammonium chloride is the largest contributor to aerosol water in Delhi, making up 40% on average, and we highlight that regulation of chlorine-containing precursors should be considered in mitigation strategies.

Severe events of wintertime particulate air pollution in Beijing (winter haze) are associated with high relative humidity (RH) and fast production of particulate sulfate from the oxidation of sulfur dioxide (SO2) emitted by coal combustion. There has been considerable debate regarding the mechanism for SO2 oxidation. Here we show evidence from field observations of a haze event that rapid oxidation of SO2 by nitrogen dioxide (NO2) and nitrous acid (HONO) takes place, the latter producing nitrous oxide (N2O). Sulfate shifts to larger particle sizes during the event, indicative of fog/cloud processing. Fog and cloud readily form under winter haze conditions, leading to high liquid water contents with high pH (>5.5) from elevated ammonia. Such conditions enable fast aqueous-phase oxidation of SO2 by NO2, producing HONO which can in turn oxidize SO2 to yield N2O.This mechanism could provide an explanation for sulfate formation under some winter haze conditions.

Chemical losses of ambient reactive volatile organic compounds (VOCs) is a long-term issue yet to be resolved in VOC source apportionments. These losses substantially reduce the concentrations of highly reactive species in the apportioned factor profiles and result in the underestimation of source contributions. This review assesses the common methods and existing issues in ways to reduce losses and loss impacts in source analyses and suggest research directions for improved VOC source apportionments. Positive Matrix Factorization (PMF) is now the main VOC source analysis method compared to other mathematical models. The issue in using any apportionment tool is the processing of the data to be analyzed to reduce the impacts of reactive losses. Estimating the initial concentrations of ambient VOCs based on photochemical age has become the primary approach to reduce reactive loss effects in PMF except for selecting low reactivity species or nighttime data into the analysis. Currently, the initial concentration method only considers daytime reactions with hydroxyl (•OH) radicals. However, the •OH rate constants vary with temperature and that has not been considered. Losses from reactions with O3 and NO3 radicals especially for alkene species remain to be included. Thus, the accuracy of the photochemical-age estimation is uncertain. Beyond developing accurate quantitative approaches for reactive losses, source analyses methods for the consumed VOCs and the accurate quantification of different source contributions to O3 and secondary organic aerosols are important additional directions for future research. [ABSTRACT FROM AUTHOR]

Aerosol pH is commonly used to characterize the acidity of aqueous aerosols and is of significant scientific interest due to its close relationship with atmospheric processes. Estimation of ambient aerosol pH usually relies on the thermodynamic modeling approach. In the existing chemical transport model and field observation studies, the temporal resolution of the input chemical and meteorological data into thermodynamic models varied substantially ranging from less than an hour to a year because of the inconsistency in the resolution of the original data and the aggregation of time-series data in some studies. Furthermore, the average value of aerosol pH has been represented by diverse metrics of central tendency in existing studies. This study attempts to evaluate the potential discrepancies in the calculated average aerosol pH arising from differences in both averaging metrics and temporal resolutions based on the ISORROPIA-II thermodynamic model and the example datasets prepared by the GEOS-Chem chemical transport model simulation. Overall, we find that the variation in the temporal resolutions of input data may lead to a change of up to more than two units in the average pH, and that the averaging metrics calculated based on the pH value of individual samples may be about two units higher than the averaging metrics calculated based on the activity of hydrogen ions. Accordingly, we recommend that the chosen averaging metrics and temporal resolutions should be stated clearly in future studies to ensure comparability of the average aerosol pH between models and/or observations. [ABSTRACT FROM AUTHOR]